EP0147660B1 - Méthode de mesure colorimétrique du zinc - Google Patents

Méthode de mesure colorimétrique du zinc Download PDF

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Publication number
EP0147660B1
EP0147660B1 EP84114486A EP84114486A EP0147660B1 EP 0147660 B1 EP0147660 B1 EP 0147660B1 EP 84114486 A EP84114486 A EP 84114486A EP 84114486 A EP84114486 A EP 84114486A EP 0147660 B1 EP0147660 B1 EP 0147660B1
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Prior art keywords
surface active
zinc
active agent
coloring
salt
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EP84114486A
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EP0147660A3 (en
EP0147660A2 (fr
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Fujio Yamazato
Kuniaki Tokuda
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Fujifilm Wako Pure Chemical Corp
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Wako Pure Chemical Industries Ltd
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/84—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving inorganic compounds or pH
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators

Definitions

  • the present invention relates to a novel method for colorimetrically measuring zinc in the presence of Fe, Cu, Co or Ni.
  • zinc is a metal present in a small amount in the living organisms and one of the indispensable metal elements necessary for the growth, and is widely distributed in the bodies of the living organisms. It has been lately reported that the concentration of zinc in serum decreases in positive acrodermatitis, taste impediment, SLE (systemjc lupus erythematosus), that zinc deficiency symptoms are observed in the case of administration of a high calorie transfusion, and so on, and the necessity of the measurement of the zinc in serum has been felt in the diagnosis, treatment and prognosis of these diseases.
  • SLE systemjc lupus erythematosus
  • the atomic absorption method, the flame photometric method, and the colorimetric measuring method are mainly used, and the colorimetrically measuring method is advantageous from the standpoint that a number of specimens to be examined can be promptly treated and no special analysis device is necessary.
  • the colorimetric reagent use may be mainly made of dithizone, zincon, PAN ⁇ 1-(2-pyridylazo)-2-naphthol ⁇ , but any one of them is not necessarily complete from the viewpoint of specificity. Further, the cyano compound or a variety of masking agents are required to be used in combination or extraction with an organic solvent is necessary in order that the interference of iron, copper, cobalt and manganese may be removed.
  • the present inventors have noted the compounds disclosed in Japanese Laid-Open Patent Application No. 91,975/1982 which have been developed as a high sensitivity colorimetrically measuring reagents for a small amount of a metal and have a molecular absorption coefficient of 7.0 - 13.3 x 10- 4 . Although these compounds are all useful as high sensitivity colorimetrically measuring reagents for the heavy metal, they have the deficiency that they are also sensitive for small amounts of a metal other than zinc, especially in the case of pyridylazoaminophenol compounds.
  • citrates condensed phosphates, sodium fluoride, nitrilotriacetic acid and 1-hydroxyethane-1,1-diphosphonic acid as the masking agents for iron
  • salicylaldoxime 2-mercaptobenzothiazol, dithiocarboxysarcosine, and dithiocarboxy glycine as the masking agents for copper
  • dithiocarboxysarcosine and 2-mercaptobenzothiazol as the masking agents for cobalt.
  • the method for colorimetrically measuring zinc using as a coloring reagent an aqueous solution of a 2-pyridylazoaminophenol derivative represented by the general formula (I): wherein X and Y represent a halogen atom or a hydrogen atom R 1 represents a hydrogen atom or a C 1 - 4 - alkyl group, and R 2 and R 3 represent a hydrogen atom, a C 1 - 4 -alkyl group, ⁇ (CH 2 ) n SO 3 H in which n is an integer of 1-4, in which I is an integer of 0-4 and m is an integer of 0-4 provides that at least one of R 2 and R 3 is -(CH 2 ) I S0 3 H or or a salt thereof, is characterized in that one or more kinds of surface active agents are used as a masking agent for Fe, Cu, Co and Ni.
  • the present inventors have made various thorough studies and examinations of a method of colorimetrically measuring zinc using as a coloring reagent an aqueous solution of a 2-pyridylazoaminophenol derivative represented by the following formula (I): as defined above and found that a surface active agent exhibits a great effect as a masking agent for Fe, Cu, Co or Ni.
  • the present invention relates to a method of colorimetrically measuring zinc by using an aqueous solution of a 2-pyridylazoaminophenol derivative represented by the general formula (I) or the salt thereof as a coloring reagent, wherein one or more kinds of surface active agents are used as a masking agent for the above specified metals.
  • the surface active agents are used in the colorimetrically analyzing method of the prior art as a solubilizing agent for coloring reagents hard to dissolve, and for the purpose of shifting of absorption wavelength and prevention of turbidity of the sample, clarification of the sample, stabilization of color development, isolation of the intended metal from the metal combined protein or extraction of produced chelate into an organic solvent.
  • the present inventors have found that the surface active agents can be used for a purpose quite different from the above-mentioned ones, that is, they can act as the masking agent for the above-specified metals.
  • the surface active agents used in the present invention are not specifically restricted, and those that dissolve to a clear solution in a range of pH 4-10, which is appropriate for the coloring reagent, are preferred.
  • nonionic, cationic and amphoteric surface active agents are preferable because they do not interfere with the coloring of zinc, and inhibit the coloring or iron, copper, cobalt and nickel. Further similar effects can be obtained when the anionic surface active agent and the nonionic surface active agent are used in combination. When these surface active agents are used together with the conventional masking agent, the effects of the above-mentioned surface active agents are remarkably increased.
  • nonionic surface active agents particularly effective for the present invention use may be made of Triton X-100 (polyoxyethylene iso-octylphenyl ether, Rohm & Haas Co., Ltd., trade name) Brij-35 (polyoxyethylene lauryl ether, Kao Atlas Co. Ltd., trade name), Emulgen 120 (polyoxyethylene lauryl ether, Kao Atlas Co. Ltd., trade name), Tween 20 (polyoxyethylensorbitan monolauryl ether, Kao Atlas Co. Ltd., trade name), Tween 80 (polyoxyethylene sorbitan monooleyl ether, Kao Atlas Co.
  • Triton X-100 polyoxyethylene iso-octylphenyl ether, Rohm & Haas Co., Ltd., trade name
  • Brij-35 polyoxyethylene lauryl ether, Kao Atlas Co. Ltd., trade name
  • Emulgen 120 polyoxyethylene lauryl ether, Kao Atlas
  • Softanol 90 polyoxyethylene alkyl ether, Nippon Catalyst Chemical Industries Ltd.), Triton X-405 (polyoxyethylene, Rohm & Haas Co., Ltd., trade name), Emulgen 147 (polyoxyethylene lauryl ether, Kao Atlas Co., Ltd., trade name), Emulgen 920 (polyoxyethylene lauryl ether, Kao Atlas Co., Ltd., trade name), Emulgen 950 (polyoxyethylene nonylphenyl ether, Kao Atlas Co., Ltd., trade name), Emulgen PP 290 N(oxyethylene-oxypropylene block polymer, Kao Atlas Co., Ltd., trade name) and Emusol 3130 (polyoxyethylenesorbitanemonostearate, Kao Atlas Co., Ltd., trade name).
  • the anionic surface active agents use may be made of Sundet EMN (polyethylenealkyl ether sulfuric acid ester sodium salt, Sanyo Kasei Kogyo Co., Ltd., trade name), Emarl NC (polyoxyethylenealkylphenyl ether sulfuric acid ester, Kao Atlas Co., Ltd., trade name), Aranon ACE (N-cocoyl-N-methyl-(3- alanine sodium salt, Kawaken Fine Chemical Co., Ltd., trade name), Emarl 20 C (polyoxyethylene alkylsulfate sodium salt, Kao Atlas Co., Ltd., trade name), Nonipol S-40 (polyethylene alkylphenyl ether sulfuric acid ester sodium salt, Sanyo Kasei Kogyo Co., Ltd., trade name), sodium lauryl sulfate (sodium salt of lauryl sulfuric acid ester), Sundet BL (alkylbenzene sulfonic acid formalin condens
  • Cotamine 24P (lauryltrimethylammonium chloride, Kao Atlas Co., Ltd., trade name)
  • Cotamine 86P stearyltrimethylammonium chloride, Kao Atlas Co., Ltd., trade name
  • Levasorp NL (laurylpyridinium bromide, Miyoshi Yushi Co., Ltd., trade name).
  • amphoteric surface active agents use may be made of Anhitol 24B (laurylbetaine, Kao Atlas Co., Ltd., trade name) and Anhitol 86B (stearylbetaine, Kao Atlas Co., Ltd.).
  • the effective concentration of the surface active agent in the present invention is not specifically restricted, 0.01-20.0% is preferred.
  • the 2-pyridylazoaminophenol derivative of general formula (I) as defined above or the salt thereof used as a coloring reagent has a partial structure as a chromophore:
  • Typical compounds include for instance:
  • the compounds in which the ortho position to an azo group of a benzene ring is substituted by a carboxyl group or an amino group are not necessarily satisfactory for the method of the present invention, and the substituting group is a hydroxy group.
  • X and Y of the general formula (I) are halogen atoms
  • the compounds are most easily synthesized when the halogen atoms are bromine atoms, and when they are chlorine, the synthesis is easier next to the former case.
  • the number of carbons in the alkyl groups of R 1 , R 2 and R 3 is 1-4.
  • the salt of the coloring reagent of the general formula (I) according to the present invention is an organic amine salt such as diethyl-amine salt or triethylamine salt, an inorganic salt such as ammonium salt, alkali metal salt or alkaline earth metal salt.
  • organic amine salt such as diethyl-amine salt or triethylamine salt
  • inorganic salt such as ammonium salt, alkali metal salt or alkaline earth metal salt.
  • those compounds of the general formula (I) in which at least one of R 2 and R 3 has a sulfonic acid group are soluble in water. They are therefore suitable for use in the present invention.
  • the present inventors have further made thorough studies as regards the methods of microanalysis which are specific to zinc and are high in sensitivity, and as a result they have found that when dimethylglyoxime which has conventionally been used as a coloring reagent of nickel is used together with the coloring reagent of the invention and the surface active agent, dimethylglyoxime surprisingly becomes an effective masking agent for nickel and cobalt. Based on this finding, the present inventors have accomplished novel and useful embodiments of the present invention in which the compound which has not been used as the masking agent in the conventional analysis method is used as the masking agent for nickel and cobalt.
  • the present invention relates also to a method of colorimetrically measuring zinc in which one or more kinds of the surface active agents are used together with 2-pyridylazoaminophenol derivative of formula (1) as defined above or the salt thereof as a coloring reagent, and dimethylglyoxime is used as an additional masking agent for nickel and/or cobalt.
  • Dimethylglyoxime used in the present invention which is a masking agent for nickel and/or cobalt is generally used in a free form or as disodium salt or in a mixed form thereof depending on the case, and may be used in a coloring reagent solution ordinarily at the concentration of 0.005-1.0%, preferably at the concentration of 0.01-0.5%.
  • the masking agents of other metals are determined depending upon the masking effect, the influence thereof upon zinc, the solubility and so forth.
  • salicyaldoxime when used as the masking agent for copper, it is used ordinarily at the concentration of 0.005-0.5%, preferably at the concentration of 0.01-0.3%.
  • a citric acid salt when used as the masking agent iron, it is used ordinarily at the concentration of 1.0-8.0%, preferably at the concentration of 2.0-5.0%.
  • the compounds exemplified in the first aspect of the present invention are used preferably too.
  • the addition amount of these compounds are the same as mentioned above.
  • a sample is serum
  • protein is removed therefrom, and then the sample is added to a reagent of the present invention in which the respectively appropriate amounts of the surface active agent and the coloring reagent are dissolved into an aqueous buffer solution of a given pH, or a reagent of the second aspect of the present invention in which an appropriate amount of dimethylglyoxime is dissolved into the former reagent, and the thus obtained solution is left for a short time, for example, 5 or 10 minutes.
  • absorbance is measured at 555 nm with reference to a reagent blank as control, and the concentration of zinc in the sample is determined from comparison with a calibration curve.
  • Table 1 differences in coloring degree among the coloring reagents with the respective metal ions depending upon the presence or the absence of the surface active agents.
  • the coloring degrees of the respective metals are changed by the addition of the surface active agents, and particularly the coloring degree of Fe is lowered to about one fourth when Brij-35 was added, thereby relatively enhancing the specificity of zinc.
  • the specificity to zinc is notably enhanced by the addition of the surface active agents.
  • the method of the present invention is excellent in reducing the coloring of iron and copper.
  • the coloring degree of iron is 13 provided that iron is added in an amount of twice by weight as large as that of each of the other metal, and that of copper is 4, while the coloring degree of zinc is 100.
  • Brij-35, Emulgen 120, Tween 80, Emusol 3130, sodium lauryl sulfate (SLS), Levenol WX, Demol N, Cotamine 24P, or Anhytrol 24B was added in an amount of 1.6%
  • the coloring degree of iron is 1-3
  • that of copper is 0-2
  • the coloring degree of zinc is 100.
  • the specificity to zinc is primarily enhanced. Since no practical problems rise in the clinically chemical analysis when the coloring of iron and copper is inhibited, this is an extremely important effect.
  • Table 4 are shown the coloring percentages of the respective metals with respect to those in Reference Example 1, and the relative values of the metals when the coloring degree of zinc is taken as 100. (In the upper lines of the column "Coloring percentage” are shown the coloring percentages of the respective metals with respect the the coloring percentages in Reference Example 1, whereas in the lower lines are given the relative values of the respective metals when the coloring degree of zinc is taken as 100).
  • the coloring percentage of zinc is 0-1% when the anionic surface active agent was used singly, when the nonionic surface active agent is coexistent, zinc is removed form masking and cobalt is further masked.
  • the quantitative measurement of zinc can be accurately performed by appropriately selecting and combiningly using dimethylglyoxime, the conventionally used masking agent and the surface active agents.
  • Results are shown in Table 7 while being compared with those according to the atomic absorption method.

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Claims (7)

1. Procédé de mesure ou détermination colorimétrique du zinc, par utilisation d'une solution aqueuse d'un dérivé de 2-pyridylazoaminophénol représenté par la formule générale (1) suivant:
Figure imgb0026
[dans laquelle X et Y représentent chacun un atome d'halogène ou un atome d'hydrogène; R1 représente un atome d'hydrogène ou un groupe alkyl en C1 à C4, et R2 et R3 représentent chacun un atome d'hydrogène, un groupe alkyle en C1 à C4, ―(CH2)n―SO3H où n est un nombre entier valant 1.à 4, ou
Figure imgb0027
où 1 est un nombre entier valant 0 à 4, et m est un nombre entier valant 0 à 4, à la conditon qu'au moins l'un des symboles RZ et R3 représente ―(CH2)n―SO3H ou
Figure imgb0028
ou un de ses sels comme réactif de coloration, procédé caractérisé en ce qu'on utilise un ou plusieurs genres d'agents tensio-actifs comme agent de masquage de Fe, de Cu, de Co et de Ni.
2. Procédé de mesure ou détermination colorimétrique selon la revendication 1, dans lequel on utilise l'agent tensio-actif en combinaison avec, et en plus, des agents classiques de masquage de Fe, Cu, Co et Ni.
3. Procédé de mesure ou détermination colorimétrique selon la revendications 1 et 2, dans lequel on utilise un agent tensio-actif non ionique comme agent tensio-actif dans le procédé de mesure ou détermination colorimétrique du zinc, en utilisant, comme réactif de coloration, un dérivé de 2-pyridylazoaminophénol représenté par la formule générale (I) ou un de ses sels.
4. Procédé de mesure ou détermination colorimétrique selon les revendications 1 et 2, dans lequel on utilise un agent tensio-actif catoinique comme agent tensio-actif dans le procédé de mesure ou de détermination colorimétrique du zinc, en utilisant comme réactif de coloration un dérivé de 2-pyridylazoaminophénol, représenté par la formule générale (I), ou son sel.
5. Procédé de mesure ou détermination colorimétrique selon les revendications 1 et 2, dans lequel on utilise un agent tensio-actif amphotère comme agent tensio-actif dans le procédé de détermination ou mesure colorimétrique du zinc, en utilisant comme réactif de coloration un dérivé de 2-pyridylazoaminophénol représenté par la formule générale (I) ou un de ses sels.
6. Procédé de détermination ou mesure colorimétrique selon les revendications 1 et 2, dans lequel on utilise un agent tensio-actif anionique et un agent tensio-actif non ionique, en combinaison, pour constituer l'agent tensio-actif dans le procédé de mesure ou. détermination colorimétrique du zinc, en utilisant, comme réactif de coloration, un dérivé de 2-pyridylazoaminophénol, représenté par la formule générale (I) ou un de ses sels.
7. Procédé pour mesurer ou déterminer colorimétriquement le zinc, en utilisant comme réactif de coloration un dérivé de 2-pyridylazoaminophénol représenté par la formule générale (I) suivante:
Figure imgb0029
selon la définition donnée à la revendication 1, et en utilisant un ou plusieurs genres d'agent tensio-actif en combinaison avec ce réactif de coloration, procédé dans lequel on utilise la diméthylglyoxime comme agent de masquage du nickel et/ou du cobalt.
EP84114486A 1983-12-02 1984-11-29 Méthode de mesure colorimétrique du zinc Expired EP0147660B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84114486T ATE47916T1 (de) 1983-12-02 1984-11-29 Verfahren zur kolorimetrischen messung von zink.

Applications Claiming Priority (2)

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JP58228221A JPS60120249A (ja) 1983-12-02 1983-12-02 亜鉛の比色定量方法
JP228221/83 1983-12-02

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EP0147660A2 EP0147660A2 (fr) 1985-07-10
EP0147660A3 EP0147660A3 (en) 1986-04-09
EP0147660B1 true EP0147660B1 (fr) 1989-11-08

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US4789525A (en) * 1987-06-22 1988-12-06 Eastman Kodak Company Analytical method and multilayer element for total ionic iron determination
JP2547664B2 (ja) * 1990-10-20 1996-10-23 富士写真フイルム株式会社 鉄イオン分析用乾式分析要素
GB0406770D0 (en) * 2004-03-25 2004-04-28 Customs & Excise Hydrocarbon markers
WO2007097468A1 (fr) * 2006-02-23 2007-08-30 Shino-Test Corporation Procede de detection d'un metal par colorimetrie et reactif de detection
JP5622144B2 (ja) * 2009-06-04 2014-11-12 国立大学法人埼玉大学 亜鉛の簡易定量法
GB201017553D0 (en) * 2010-10-18 2010-12-01 Univ Cardiff A method and device for detecting alkylating agents
CN114280043B (zh) * 2021-12-24 2023-11-03 郑州安图生物工程股份有限公司 一种防低温沉淀的精浆锌显色液及其制备方法和应用

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JPS5930061A (ja) * 1982-08-12 1984-02-17 Wako Pure Chem Ind Ltd 微量金属の比色定量方法

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Anal Chim ACTA 1983,149,269-79 *

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DE3480431D1 (en) 1989-12-14
JPH0340828B2 (fr) 1991-06-20
EP0147660A3 (en) 1986-04-09
JPS60120249A (ja) 1985-06-27
EP0147660A2 (fr) 1985-07-10
ATE47916T1 (de) 1989-11-15

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